March, 1951
1149
ARYLATIONS OF p-QUINONE DIBENZENESULFONIMIDES
n 2 ml. of dry chloroform. The h k was stoppered immediately and shaken vigorously. After about twenty minutes, the adduct began t o crystallize. The reaction mixture was permitted to stand at room temperature for 48 hours. The crystalline material present was collected by filtration and dried in the air; yield 1.25 g. (87%). This product was washed with two 7-8 ml. portions of boiling dry chloroform and was then recrystallized from hot dry chloroform t o which sufficient dry ethyl acetate was added t o effect complete solution. Further recrystallization from chloroform-ethyl acetate gave :he analytically pure ihiophenol adduct, m. p. 189-190.5 , with softening at 187 Anal. Calcd. for C,*Ht.NOS: C. 60.48: H. 4.23: N. 3.92. Found: C, 60.%i;-H, 4.51; N, 3.78: ' Attempted Addition of Morpholine to $-Quinone Monobenzenesulf0nimide.-To a solution of 1 K. of the auinone imide in 10 ml. of dry chloroform was adaed a chl6roform solution of 0.4 g. of morpholine. The resulting mixture became violet in color, then greenish-black. The reaction mixture was permitted t o stand 48 hours and was then evaporated t o dryness. The tarry residue was dissolved in 5% aqueous sodium hydroxide (Darco) Dilute hydrochloric acid was added dropwise with stirring t o the alkaline solution, until a pH of approximately 7.5 was reached. A tar resulted, which resisted all attempts a t crystallization. Reduction of -Quinone Monobenzenesulfonimide with Sodium Hydros&te.- To an absolute ethanolic solution of 0.5 g. of the quinone imide was added sufficient 10% aqueous sodium hydrosulfite t o effect decolorization. Inorganic material was removed by filtration and the filtrate was evaporated t o dryness. The residue was washed with water, filtered and dried in the air; yield 0.4 g. Recrystallization from ethyl acetate gave p-benzenesulfonamidophenol, m. p. 154-155', not depressed upon admixture with authentic material.
.
I
,
.
{CONTRIBUTION FROM THE
Hydriodic Acid Reduction of +-Quinone Monobenzene sulfonimide.-To 5 ml. of concd. hydriodic acid (sp. gr. 1.50) was added 0.5 g. of solid p-quinone monobenzenesulfonimide. An instant liberation of iodine occurred. The reaction mixture was heated on the steam-bath for 30 minutes. The crude product was collected by filtration, washed with water, dried in the air and washed with chloroform; yield 0.3 g. Recrystallization from ethyl acetake gave pure p-benzenesulfonamidophenol, m. p. 155-156 , unchanged upon admixture with authentic material. Hydrolysis of p-Quinone Monobenzenesulfonimide .-A suspension of 0.5 g. of the quinone imide in 20 ml. of water was heated under reflux over a low fiame for 45 minutes. The reaction mixture was cooled and the crystalline material present was collected by filtration and dried in the air; yield 0.2 g. Recrystallization from dilute ethanol gave a virtually colorless compound, m. p. 151-152', not depressed upon admixture with authentic benzenesulfonamide, m. p. 152-153'. A depression of 30" was obtained up2n admixture with p-benzenesulfonamidophenol, m. p. 156 A small quantity of p-benzoquinone, m. p. 110-114",collected in the lower part of the condenser tube. Further evidence for the presence of quinone was found in the detection of its characteristic odor in the reaction mixture and in the steam volatility of the reaction product remaining in the reaction mixture after removal of the benzenesulfonamide. Hydrolysis of 3 -Methyl-p-quinone 1-Benzenesulfonimide -A suspension of 1.0 g. of the quinone imide in 40 ml. of water was heated under reflu: for 15 minutes. A quantity of p-toluquinone, m. p. 67-68 ,collected in the lower part of the condenser. Upon cooling, solid material separated from the reaction mixture. Recrystallization from benzene gave nicely crystalline material, m. p. 14&150", not depressed upon admixture with authentic benzenesulfonamide. RECEIVED JULY 27, 1950 URBANA, ILL.
.
.
NOYESCHEMICAL LABORATORY, UNIVERSITY
OF
ILLINOIS]
Quinone Imides. V. Aluminum Chloride-catalyzed Arylations of p-Quinone Dibenzenesulfonimides B Y ROGERADAMS AND KENDRICK R. EILAR Aromatic hydrocarbons, phenols and phenolic ethers in the presence of aluminum chloride react with p-quinone dibenzenrsulfonimides t o give 2-aryl-p-phenylenedibenzenesulfonamides in yields of 26 to 67y0. In the addition of bydrocarbons, it is essential that the quinone diimide be added to the aluminum chloride in the hydrocarbon ; addition of the aluminum chloride to the hydrocarbon solution of the quinone diimide results in quantitative reduction of the quinone diimide to p-phenylenedibenzenesulfonamide. Boron trifluoride, as catalyst, is effective in the addition of phenolic compounds and phenol ethers but not of the hydrocarbons regardless of the order of addition of reactants. Attempted oxidation of the S-aryl-p-phenylenedibenzenesulfonamides to the corresponding quinones was successful only in the case of 2-(,3-hydroxy-a-naphthyl)compound ; the other sulfonamides either resisted oxidation or were degraded to p-quinone dibenzenesulfonimide.
Pummerer and co-workers discovered that a variety of aromatic compounds in the presence of aluminum chloride will add, presunlably by a 1,4 process, t o p-benzoquinone to give 2,5-diarylhydroquinones.' This reaction has now been extended to pquinone dibenzenesulfonimide (I).z The arylation NHSOzCsHa
s;JSOzCeHs
I
,
NSOsCsHs I
NHSO~C~HI I1
(1) R. Pummerer and E. Prell. Bcr., 60, 3105 (1922); R. Pummerer and H. Fiedler, ibid., 60, 1439 (1927); R. Pummerer and G. Huppmann, ibid., 60, 1443 (1927); R. Pummerer, M. Dally and S. Reissinger, ibid., 66, 792 (1933). (2) R. Adams and A S . Nagarkatti, THIS J O U R N A L , 79, 4601 (1950); see also R. Adams and J L. Anderson, ibid., 73, 5154 (1950); R. Adams and R. A, Wankel, ibjd., 73, 131 (1951); R Adams and J . H. Looker, ibid., 75, 1145 (1951).
of the quinone diimide terminates with the monosubstituted p-phenylenediamine derivative; thus, reaction of p-quinone dibenzenesulfonimide (I) with benzene gives 2-phenyl-p-phenylenedibenzenesulfonamide (11, R = H) in 67y0 yield, when the quinone diimide is added t o a mixture of aluminum chloride in benzene. When the addition is reversed, the introduction of aluminum chloride to a solution of the quinone diimide in benzene, reduction takes place quantitatively with formation of the parent p-phenylenedibenzenesulfonamide. The oxidation product of the benzene in the latter reaction was presumably biphenyl, although i t was not isolated and identified. The reaction of m-xylene with I, carried out by adding the quinone diimide to a mixture of aluminum chloride in m-xylene, gives a mixture of products. Three were isolated; one was the expected adduct (III), the second, p-phenylenedibenzenesulfonaniide formed by reduction of the quinone di-
1150
ROGERADAMSAND KENDRICK R. EILAR
Voi. 78
imide, and the third, a hydrocarbon (IV) formed by the oxidation of the m-xylene.
quinone diimide are thus unquestionably phenols, exemplified by I1 (R = OH), and not diary1 ethers. The crude products obtained from the phenolic NHSOPCGHI NHSOtC6Hs ethers (anisole, phenetole and veratrole) and the quiI none diimide contain merely traces of ether cleavage compounds as shown by the very faint color tests. Oxidation of 2-phenyl-$-phenylenedibenzenesulfonamide took an unexpected course. It did not give the corresponding quinone diimide but resulted in a cleavage of the molecule with elimination of the phenyl ring and formation of p-quinone dibenzenesulfonimide. The analogous oxidation occurred, although in poorer yield, with 2-($-hydroxyphenyl) - p - phenylenedibenzenesulfonamide. Iv The product (11, R = OCHa) from anisole resisted oxidation even over a long period of time. The The oxidation product of the m-xylene was a liquid of empirical formula ClsHls whose physical acetate of I1 (R = OH) was also recovered after properties did not correspond to those of 2,2f,4,4f- refluxing for 16 hours with lead tetraacetate in glatetramethylbiphenyl. It proved to be 2,3',4- cial acetic acid solution. Attempted oxidation of trimethyldiphenylmethane (IV). Compound I V this compound with chromic acid was unsuccessful. was synthesized by an unequivocal method, the The only 2-arylated p-phenylenedibenzenesulfoncondensation of m-xylyl chloride with m-xylene in amide which was successfully oxidized to its quipresence of aluminum amalgam and shown to be none was 2-( P-hydroxy-a-naphthyl) -p-phenylenediidentical in physical properties and ultraviolet benzenesulfonamide, although it was never obspectrum with the isolated by-product. I t is thus tained completely pure. The 2-methyl-$-quinone dibenzenesulfonimide probable that the quinone diimide in presence of reacted with 0-cresol t o give 2-methyl-5-(3-methylaluminum chloride converted part of the m-xylene to the m-xylyl radical which reacted with the rn- 4 - hydroxyphenyl) - p - phenylenedibenzenesulfonamide. The 2-chloro-p-quinone dibenzenesulfonxylene used as solvent to form IV. When boron trifluoride is substituted for alumi- imide, however, gave with anisole and o-cresol only num chloride as catalyst, by bubbling the former intractable tars. All of the aluminum chlorideinto a solution of the quinone diimide in benzene or and boron trifluoride-catalyzed reactions were by introducing the boron trifluoride into the ben- characterized by a certain amount of tar formation. zene and adding the quinone diimide, the p-quinTABLE I one diimide is reduced quantitatively to p-phenyl- A D I J I ~ ~ OPRODUCTS* Y OF ~ Q U I N O S E DIBESZENESULFOSenedibenzenesulfonamide. Reduction of the quiIMIDES IN PRESENCE OF AIC13 none diimide also occurs exclusively when boron trip-Phenylenedibenzenesnlfon- Yield, M. p 'C. Analyses, yo fluoride is passed into a solution of quinone diimide Calcd Found Adduct amide % (cor.) in m-xylene. Benzene 2-Phenyl67 196 C, 62.05 61.92 Several phenols and phenol ethers were found t o H , 4.34 4.55 react with the quinone diimide in the presence of m-Xylene 2-(2,4-Dirnethyl- 26 196 sl. dec. C, 63.39 63.28 phenyl)H , 4.91 5.09 aluminum chloride or boron trifluoride to give com227-228 dec. C, 60.00 59.83 2 ($-Hydroxy63 pounds of the type shown in I1 in yields of 27 to Phenol phenyl)H, 4 . 2 0 4.42 67Yo0. The adduct, (11, R = OH), produced when o-Cresol 2 (3-Methyl-4-hy- 67 217-218 dec. C, 60.70 60.54 droxyphenyl) phenol was used, contains a free hydroxy group as H, 4.48 4.66 C, 60.70 60.93 proved by conversion into the corresponding ace- In-Cresol 2-(2-Methyl-4-hy- 27 175 droxyphenyl)-b 4.58 H, 4.48 tate. The position of the hydroxy group was not 8-Naph- 2-(&Hydroxy41 237-238 dec. C, 63.38 63.03 established, but by analogy with the products in tho1 a-naphthyl)H, 4.18 4.06 the benzoquinone series' it is reasonable to expect Anisole 2-(p-Methoxy- 61 5 193-195 dec. C, 60.70 60.72 phenyl)-c H, 4.48 4.52 that the hydrogel1 para to the hydroxy has taken 50 188-189 dec. C, 61.38 61.01 part in the addition reaction. 0- arid m-cresol and Phenetole P-(p-Bthoxyphenyl)H , 4.95 4.94 8-iiaphthol react in a similar way to give products Veratrolc 2-(3,4-Dimeth- 25 197-198 dec. C, 59.59 60.07 oxyphenyl)analogous to 11; $-cresol, however, did not add to H , 4.59 4.72 the quinone diimide but induced reduction of the These reactions were all carried out in essentially the quinone diimide to the 9-phenylenediamine deriva- s a n e manner as that described in the Experimental section the preparation of 2-phenyl-p-phenylenedibenzenetive. Neither the product of phenol and the for sulfonamide. In cases where the aromatic reactant was a quinone diimide nor those obtained from 0- and m- solid, carbon disulfide was used as solvent, and a four-mole cresol and /3-naphthol give a color with ferric chlo- excess of the aromatic compound was used. This comride; however, they all give a definite coloration in pound crystallized from ethanol with one molecule of of crystallization; in this form it melted at 114the phosphomolybdic acid test for hindered phenol^.^ ethanol 115O,then upon further heating solidified and finally melted The products from anisole, phenetole and veratrole, at 175'. Anal. Calcd. for ~&&Nz&C&I6OH: C, as well as the acetate of I1 (R = OH), give nega- 60.00; H, 5.23. Found: C, 60.32; H, 5.35. A sample was heated in vacuo at 140" for 6 hours; wt. sample, 0.2252 tive phosphomolybdic acid tests. The biphenyls loss in weight, 0.0191 g.; calcd loss in weight for one derived from the addition of various phenols to the g.; molecule of ethanol 0 0191 g. By use of boron tri-
.
31 F Lllmann and G h i Meyer, A ~ z M332, , 45 (1904) 4 ) K Hrnuer Ckeni Zf6 60, 537 (1926)
fluoride in place of aluminum chloride, the same product w.15 ol,t:tined i i i 5zf: yield
March, 1951
1151
ARYLATIONS OF $-QUINONEDIBENZENESULFONIMIDES
reduced pressure on the water-bath. The dark colored residue was extracted with ether, leaving 3.3 g. (26%) of 2(2,4 dimethylphenyl) p - phenylenedibenzendonamlde. Recrystallization from ethanol gave pure white crystals, m. p. 196" (cor.) with slight decomposition. When boron trifluoride was used only reduction occurred. A suspension of 6 g. of #-quinone dibenzenesulfonimide in 100 ml. of redistilled m-xylene in a 200 ml., 3-necked flask fitted with a stirrer, calcium chloride tube and a glass tube Experimental whose outlet dipped just below the surface of the solution, #-Quinone Dibenzenesulf0nimide.-This product was was cooled in a n ice-bath. Boron trauoride was admitted prepared in earlier work by the oxidation of p-phenylenedi- through the glass tube until fumes began emerging from benzenesulfonamide in glacial acetic acid with lead tetraace- the calcium chloride tube. The boron trifluoride was turned tate. A somewhat cheaper and indeed more convenient off and stirring was continued for one-half hour. The soluprocedure for preparing large quantities has now been tion was liltered and the purple solid was washed with found. It employs pure red lead in place of lead tetra- ethanol, and dried in an oven a t 110", yielding 6 g. (100%) acetate. Some grades of red lead are better than others and of p-phenylenedibenzenesulfonamide, m. p. 247-249 consequently that which proved best is indicated. The use When mixed with an authentic sample1 the melting point of less suitable grades of red lead result in quinone diimide of was not depressed. lower purity which requires an additional crystallization or 2,3',4-Trimethyldiphenylmethane.-(A) The ether extwo before it is pure. This reaction was first performed by tract described above in the aluminum chloride experiment Dr. C. Robert Walter, Jr. was distilled at reduced pressure ; the distillate weighing A suspension of 43 g. of p-phenylenedibenzenesulfonamide 1.4 g. was a clear, cdlorless oily liquid, b. p. 122-125' at 2 in 500 ml. of glacial acetic acid in an 800-ml. beaker was mm. (309' a t 757 mm. by a micro determination); nZoD heated to and maintained a t 65' with continuous stirring 1.5630; d', 1.0523; it did not solidify when cooled t o 0". while 76.2 g. of red lead (Pbz04, Baker Analyzed) was added Anal. Calcd. for CleH18: C, 91.43; H, 8.57. Found: in portions over a period of 45 minutes. The yellow a s - C, 91.41; H, 8.57. pension was then cooled in an ice-bath for an hour, after (B) m-Xylyl chloride6 was condensed with m-xylene by which it was filtered. The crude product weighed 41 g. (96%), m. p. 167-178'. To purify, 150 ml. of glacial ace- the use of amalgamated aluminum according t o the procetic acid was heated t o boiling, the crude quinone was added, dure given by Hartman and Phillips6 for the preparation of and the solution stirred for 1 minute, filtered and quickly diphenylmethane from benzyl chloride and benzene. It cooled. The product amounted t o 36.3 g. (85%)! rn: p. was not necessary t o reflux the reactants, however; the re178-179 O (cor.). One to four additional crystallizations action commenced immediately upon mixing a t room temraise the melting point to a maximum of 188" (cor.), the perature. The crude yield of 2,3 ',4-trimethyldiphenylnumber necessary depending upon any particular prepara- methane was 84%; one distillation gave pure material in tion. Product, m. p. 178-179", is entirely satisfactory for 60% yield, 123-125' a t 2 mm., nZoD1.5641. A d . Calcd. for Cl&la: C, 91.43; H, 8.57. Found: subsequent reactions. The product, m. p. 188", appears to be relatively stable at C, 91.02;. H,. 9.04. room temperature and the melting point is only slightly The ultraviolet absorption spectrum of the synthetic lower after two months. A less pure sample, however, de- material was identical with that of the hydrocarbon proteriorates more rapidly and the Felting point in a few duced in the reaction of the p-quinone dibenzenesulfonimide These older samples with m-xylene in presence of aluminum chloride. months may be as low as 150-160 are readily purified to the maximum melting point by crysL-(p-Acetoxyphenyl) -p-phenylenedibenzenesulfonamide tallization from glacial acetic acid. -To a solution of 2 g. of 2-($-hydroxyphenyl) +phenylene2-Phenyl-p-phenylenedbenzenesulfonamide.-To 100 dibenzenesulfonamide in 10 ml. of pyridine, 25 ml. of acetic ml. of dry benzene in a 400-ml. beaker cooled by an ice-bath anhydride was added and the mixture allowed t o stand a t was added with stirring 15 g. of anhydrous aluminum chlo- room temperature for 24 hours. It was then poured onto ride. After 15 minutes of continued stirring, 10 g. of p- ice. After standing 24 hour:, the white solid was collected quinone dibenzenesulfonimide' was added in portions over a by filtration and dried a t 110 The yield was 2.1 g. (97%). period of 15 minutes. The solution was then stirred for a After purification by recrystallization from ethanol, it period of 2 hours after which the ice-bath was removed. melted at 179-180 ' (cor .) After a further hour of stirring with external cooling, the Anal. Calcd. for GH22N20&: C, 59.77; H , 4.62. black solution was poured with stirring into 300 ml. of Found: C, 59.75; H, 4.71. of water and a little hydrochloric acid containing enough ice 2-( 8-Hydroxy-a-naphthyl) -#-quinone Dibenzenesulfonto prevent warming beyond room temperature. The yellow-brown solid was filtered, washed with water imide.-A suspension of 1 g. of 2-( 8-hydroxy-a-naphthyl) and air-dried. It was purified by crystallization from p-phenylenedibenzenesulfonamideand 1 g. of lead tetraethanol (Darco). The yield of once crystallized material acetate in 2 ml. of glacial acetic acid in a test-tube was was 8 g. (67%). When pure, the product formed white shaken for 15 minutes. After addition of 5 ml. of water, crysotah, m. p. 196" (cor.) with slight sintering starting a t the yellow precipitate was filtered, washed with water, and recrystallized from ethyl acetate. The yield was 0.3 g. 192 . To a suspension of 2 g. of 2-phenyl-p-phenylenedibenzene- (30%) of orange-yellow crystals, m. p. 208" (cor.) when sulfonamide in 5 ml. of glacial acetic acid was added 1.9 g. of placed in a preheated bath a t 208' (in an ordinary melting lead tetraacetate. The mixture was heated to 50" with point determination without a preheated bath, the comThe stirring for 10 minutes, then cooled in an ice-bath. The pound slowly turned tan and finally charred at 241 ') yellow crystals were filtered and washed with a little cold product was not absolutely pure as shown by analysis. Anal. Calcd. for C - B H ~ O N ~ O ~C,S ~63.62; : H, 3.82. acetic acid and then with petroleum ether (b. p. 30-60"). The yield was 1.5 g. of p-quinone dibenzenesulfonimide. Found: C, 64.40; H, 3.92. A further quantity of 0.1 g. of product was obtained by x-Chloro-( 8-hydroxy-a-naphthyl) -B-phenylenedibenzeneadding water t o the filtrate, making a total of 1.6 g. (96oJo). sulfonamide.-To a solution of 0.1 g. of 2-(p-hydroxy-aTwo recrystallizations from ethyl acetate gave matenal naphthyl) +-quinone dibenzenesulfonimide in 5 ml. of melting at 179" (cor.) with decomposition. Reduction glacial acetic acid was added five drops of concd. hydrowith aqueous sodium hydrosulfite gave p-phenylenedi- chloric acid. Complete decolorization of the solution ocbenzenesulfonamide, m. p. 247" (cor.). It did not depress curred within 3 minutes. Water was then added dropwise the melting point of an authentic sample. until a faint turbidity appeared. After standing overnight, 2 - (2,4-Dimethylphenyl) -p-phenylenedibenzenesulfon- fluffy, white crystals had formed. These were filtered, amide .-With aluminum chloride : Substitution of m-xylene washed with water and recrystallized from aqueous ethanol; for benzene in the procedure described for the preparation m. p. 214' (cor.). The product was not entirely pure. of 2-phenyl-p-phenylenedibenzenesulfonamide gave, upon (5) M. S. Khpreschand H. C.Brown, THISJOURNAL, 61,2142 (1939). hydrolysis of the reaction mixture, 5 g. of p-phenylenedi( 8 ) Phillips, "Organic Syntheses," Coll. Vol. 11, John Wiley & Sons, benzenesulfonamide which was removed by filtration. The p. 232. m-xylene layer of the filtrate was separated and distilled at Inc., New York, N. Y.,
The compounds prepared from I by aluminum chloride catalysis are summarized in Table I. The authors are indebted to Miss Emily Davis and Miss Rachel Kopel for the microanalyses and to Miss Ella Richards for the determination of ultraviolet absorption spectra.
-
-
.
.
.
.
.
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ROGERADAMSAND C . ROBERT~VALTER,JR.
1152
Anal. Calcd. for C&H2,C1N20&: C, 59.52; H , 3.75. Found: C , 58.67; H , 3.46. Attempted Preparation of 2-(p-Hydroxyphenyl) $-quinone Dibenzenesulfonimide.-A mixture of 0.5 g. of 2-(phydroxyphenyl) -#-phenylenedibenzenesulfonamide and 0.5 g. of lead tetraacetate was shaken for 1 hour a t room temperature in 20 ml. of dry chloroform. The solution was filtered, the filtrate was evaporated to dryness, and the residue was stirred with 1 ml. of ethyl acetate. The yellow solid was filtered, washed with one ml. of ethyl acetate and then recrystallized from 2 ml. of ethyl acetate. The yield was 0.1 g. (20%) of yellow crystals, m. p . 178-179" (dec.). Reduction with aqueous sodium hydrosuolfite gave 9phenylenedibenzenesulfonamide; m. p. 247 It did not depress the melting point of an authentic sample. 2-(3-
.
[C)ONTRIBUIION
FROM THE
- -
Vol. 73
- -
Methyl 4 hydroxyphenyl) # phenylenedibenzenesulfonamide gave similar results. Z-Methyl-5-(4-methyl-4-hydroxyphenyl) -p-phenylenedibenzenesulf0namide.-Following the general directions for the addition of benzene to p-quinone dibenzenesulfonimide, o-cresol was added to 2-methyl-9-quinone dibenzenesulfonimide. The product was obtained in 52% yield. It formed white crvstals. m. D. 189" (cor.) with decomDosition. Anal.- Calcd. ior C&I;2N20&: C, 61:88; €1, 4.50. Found: C, 61.49; H , 4.77. Attempted addition of o-cresol and anisole to 2-chloro-pphenylenedibenzenesulfonamide under the same conditions gave only tars.
URBANA, ILL.
RECEIVED JULY 31, 1950
NOYESCHEMICAL LABORATORY, UNIVERSITY OF ILLINOIS]
Quinone Imides. VI. Addition of Dienes to p-Quinone Sulfonimides BY ROGERADAMSAND C. ROBERT WALTER,JR. Diels-Alder reactions have been applied to p-quinone dibenzene- and dimethane-sulfonimides. They add one molecule of butadiene t o give 5,8-dihydronaphthylene-1,4-disulfonamides.The latter on addition of one molecule of bromine and dehydrohalogenation give naphthylene-l,.l-disulfonamides.2,3-Diphenylbutadiene gives a stable mono-adduct with pquinone dibenzenesulfonimide which is rearranged by halogen acid t o 6,7-diphenyl-5,8-dihydronaphthylene-l,4dibenzenesulfonamide. The methanesulfonimide does not react similarly. Two molecules of cyclopentadiene add and the products may be hydrogenated with saturation of the two carbon-carbon and two carbon-nitrogen double bonds. Anthracene does not act as a diene in the way it does with p-quinone but adds 1,4 to give 2-(9-anthryl)-P-phenylenedibenzenesulfonamide.
p-Quinone disulfonimides of various types exhibit reactions similar to p-quinones. They are reduced to the corresponding p-phenylenedisulfonamides, they add hydrogen chloride, and most of them also add amines and thiols. The application of the Diels-Alder reaction to the p-quinone disulfonimides has now been studied. When p-quinone dibenzenesulfonimide is heated in a sealed tube a t 100-llOo with butadiene in benzene, a product separates which has structure 11. Even with excess of butadiene the same product is formed. The expected intermediate addition prod-
none dimethanesulfonamide reacts similarly and the corresponding 5,8-dihydronaphthylene-1,4-dimethanesulfonamide results which is converted through addition of bromine and elimination of hydrogen bromide to the fully aromatic analog. However, in the initial addition of butadiene to the 9-quinone dimethanesulfonimide, some di-adduct was isolated, presumably with structure 111, since its infrared spectrum shows the presence of carbon-nitrogen double bonds and no NH grouping. KSOZC11~
I11
Unexpectedly, isoprene and dimethylbutadiene do not appear to behave like butadiene. Although uct (I) is apparently unstable under the conditions reaction products formed which were purified to of the reaction and is converted completely by mi- constant melting point, nevertheless they did not gration of two hydrogens into the aromatic com- show the proper analysis for 1 : l or 2 : l adducts. pound, 5,8-dihydronaphthylene-1,4-dibenzenesul-Their structures have not yet been elucidated. fonamide (11). The compound adds two atoms of 2,3-Diphenylbutadiene and p-quinone dibenbromine to the isolated double bond. This was zenesulfonimide react upon refluxing in benzene and assumed since p-quinone dibenzenesulfonamide does a yellow compound results which is apparently the not react with bromine under the same conditions. adduct analogous to I. Upon warming with a The dibromo derivative thus formed upon treat- little mineral acid, rearrangement occurs with ment with ethanolic alkali loses two molecules of formation of 6,7-diphenylnaphthylene-1,4-dibenhydrogen bromide to produce naphthylene-1,Pdi- zenesulfonamide. +Quinone dimethanesulfonibenzenesulfonamide. This latter compound was mide, however, failed t o react with 2,Bdiphenylbuidentified by comparison with an authentic sample tadiene under the same conditions. synthesized from 1,4-naphthylenediamine. p-QuiCvclopentadiene. which is a n extremely reactive (1) (a) R . A d a m and A. S. Nagarkatti, THIS JOURNAL, 71, 4601 die&, a& to the $-quinone dibenzenes;lfonimide (1950); (b) R. Adams and J. L. Anderson, ibid., 71, 5154 (1950); in benzene solution at temperature.~h~ ( c ) R. A d a m and R. A. Wankel, ibid., 73, 131 (1951); (d) R. Adams product is the di-adduct (Iv) and in no attempt and J . H. Looker, ibid., 73, 1145 (1951): (e) R . Adamsand K, R. Eilar, ibid., 73, 1149 (1951). was it possible to isolate the mono-adduct even I
I1
